Classifications

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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/16—Making expandable particles
  • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
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  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
  • C08J5/121—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives by heating
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/16—Making expandable particles
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/24—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by surface fusion and bonding of particles to form voids, e.g. sintering
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/08—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers using foamed adhesives
• • C—CHEMISTRY; METALLURGY
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/06—CO2, N2 or noble gases
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08J2207/00—Foams characterised by their intended use
  • C08J2207/02—Adhesive
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/22—Thermoplastic resins
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  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/26—Elastomers
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
  • C08J2325/02—Homopolymers or copolymers of hydrocarbons
  • C08J2325/04—Homopolymers or copolymers of styrene
  • C08J2325/08—Copolymers of styrene
  • C08J2325/10—Copolymers of styrene with conjugated dienes
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
  • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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  • C08J2400/00—Characterised by the use of unspecified polymers
  • C08J2400/22—Thermoplastic resins
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  • C08J2400/00—Characterised by the use of unspecified polymers
  • C08J2400/26—Elastomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
  • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

• the invention relates to the use of hollow particles with a shell made of thermoplastic elastomers and a gas-filled cell for the production of porous molded bodies, a process for producing porous molded bodies by thermally bonding or gluing the hollow particles and the porous molded bodies obtainable therefrom.
• Highly elastic, closed-cell foams such as particle foams made of thermoplastic polyurethane, are for example in WO 2007/082838 described.
• the molded parts obtained by welding foam particles together show good mechanical properties and high rebound resilience.
• the thickness of the outer shell of the foam particles has a great influence on the mechanical properties of the molded foam part.
• Cell wall thicknesses and the ratio of cell wall thickness to inner cell structure can only be varied slightly due to the manufacturing method. Greater wall thicknesses are therefore synonymous with a higher volume weight.
• Hybrid systems made from foamed thermoplastic elastomers (TPE) and polyurethanes are made of WO 2008/087078 known. They are available by gluing or foaming foam particles using PU binders or PU system foams.
• the DE 10 2006 046868 describes the production of a foam material from polyvinyl chloride (PVC), using, inter alia, hollow spheres with a shell made of thermoplastic polyurethane, which are filled with a low-boiling liquid.
• PVC polyvinyl chloride
• the EP 0 697 274 B1 describes open-cell expansion molded parts made of a polyolefin resin, which can be obtained by welding tubular, foamed particles with a through hole.
• the WO 2007/022338 describes a shoe with a midsole, which has a cushioning element in the form of a liquid-filled bag made of z. B. having thermoplastic polyurethane.
• Bags (airbags) filled with liquids or gas as damping elements have the disadvantage, however, that the pressure is unevenly distributed due to the size of the chambers and the entire damping element becomes unusable if one chamber is damaged.
• the object of the invention was therefore to remedy the disadvantages mentioned and to use hollow particles which can be processed into porous molded bodies which, at low density, have high compressive strength, high rebound resilience and low compression set.
• hollow particles with a shell made of thermoplastic elastomers and a gas-filled cell were used in order to produce porous moldings therefrom.
• the bulk density of the hollow particles used is preferably in the range from 30 to 500 kg / m 3 , particularly preferably in the range from 50 to 350 kg / m 3 .
• the hollow particles preferably have mean grain sizes d m in the range from 2.5 to 25 mm, particularly preferably in the range from 5 to 15 mm.
• the grain sizes can be determined by sieve analysis.
• the hollow particles can be used in monomodal, bimodal or multimodal distribution. During the production of the hollow particles, particles of different sizes and shapes can be produced.
• the mean particle diameter generally varies from 2.5 mm to 25 mm, preferably in the range from 3 to 20 mm, particularly preferably in the range from 5 to 15 mm.
• the mean particle diameter can e.g. B can be determined by measuring 100 particles and forming the mean value or by sieve analysis.
• the particles can be divided according to size by sieving with different sieves. In this way, the particles can be separated into so-called sieve fractions.
• the grain size of the hollow particles has a considerable influence on the mechanical properties of the porous molded body, but also on the amount of binder required.
• the shell of the hollow particles preferably has a wall thickness in the range from 0.02 to 2 mm, particularly preferably in the range from 0.05 to 1 mm.
• the hollow particles each have a gas-filled cell.
• the volume of these cells is preferably in the range from 1 to 10,000 mm, particularly preferably in the range from 10 to 5,000 mm 3 and very particularly preferably in the range from 100 to 1,000 mm 3 .
• thermoplastic elastomers are, for example, thermoplastic polyurethanes (TPU), thermoplastic polyester elastomers (e.g. polyether esters and polyester esters), thermoplastic block copolyamides (e.g. polyether block amides PEBA made from PA-12 segments and polyether segments) or thermoplastic styrene-butadiene block copolymers. Hollow particles based on thermoplastic polyurethane (TPU) are particularly preferred.
• thermoplastic elastomers used to produce the hollow particles preferably have a Shore hardness in the range from 25A to 82D, preferably in the range from 30A to 80D, particularly preferably in the range from 65A to 96A, determined in accordance with DIN 53505.
• Thermoplastic polyurethanes are preferably used to produce the hollow particles.
• the TPUs used are preferably based on polyether alcohol, particularly preferably polyether diol.
• Polytetrahydrofuran is particularly preferred.
• the TPU is particularly preferably based on polytetrahydrofuran with a molecular weight between 600 g / mol and 2500 g / mol.
• the polyether alcohols can be used either individually or as a mixture with one another.
• TPU based on polyester alcohol, preferably polyester diol, preferably based on adipic acid and butane-1,4-diol, with a molecular weight between 600 g / mol and 3000 g / mol.
• TPU can be prepared by reacting (a) isocyanates with (b) isocyanate-reactive compounds with a molecular weight of 500 to 10,000 and optionally (c) chain extenders with a molecular weight of 50 to 499, optionally in the presence of (d) catalysts and / or ( e) customary auxiliaries and / or additives are produced.
• chain regulators usually with a molecular weight of 31 to 499, can also be used.
• chain regulators are compounds which have only one isocyanate-reactive functional group, such as. B. monofunctional alcohols, monofunctional amines and / or monofunctional polyols.
• a flow behavior, especially in the case of TPUs, can be set in a targeted manner by such chain regulators.
• Chain regulators can generally be used in an amount of from 0 to 5, preferably 0.1 to 1, part by weight, based on 100 parts by weight of component b) and, by definition, fall under component c).
• the molecular weight data relate to the number average M n , in g / mol, unless stated otherwise.
• the structural components (b) and (c) can be varied in relatively broad molar ratios.
• Chain extenders (c) are also preferably used to produce the TPU.
• the reaction can be carried out using customary indicators, preferably an index from 60 to 120, particularly preferably an index from 80 to 110.
• the index is defined by the ratio of the total isocyanate groups of component (a) used in the reaction to the isocyanate groups reactive groups, ie the active hydrogens, components (b) and (c). With an index of 100 there is an active hydrogen atom for each isocyanate group of component (a), i.e. an isocyanate-reactive function of components (b) and (c). If the index exceeds 100, there are more isocyanate groups than OH groups.
• the TPU can be produced continuously by the known processes, for example with reactive extruders or the belt process according to the one-shot or the prepolymer process, or batchwise according to the known prepolymer process.
• the components (a), (b) and, if appropriate, (c), (d) and / or (e) reacting can be mixed with one another in succession or at the same time, the reaction commencing immediately.
• the components (a), (b) and optionally (c), (d) and / or (e) are introduced individually or as a mixture into the extruder, e.g. brought to reaction at temperatures of 100 to 280 ° C., preferably 140 to 250 ° C., the TPU obtained is extruded, cooled and granulated. If appropriate, it can be advantageous to heat the TPU obtained at 80 to 120 ° C., preferably 100 to 110 ° C., for a period of 1 to 24 hours before further processing.
• the cells of the hollow particles preferably contain oxygen, nitrogen, argon, carbon dioxide or mixtures thereof as gas.
• Tetrahedra, cylinders, spheres, lenses or polyhedra such as cubes or octahedra can be used as particle shapes.
• the hollow particles are preferably in the form of hollow cylinders or hollow tetrahedra, which can be produced from the thermoplastic elastomer by welding a hose or a film. As a bed, the hollow particles behave similarly to foam particles. In contrast to these, however, they have significantly fewer and larger cells. In the preferred embodiment with only one cell per hollow particle, their structure corresponds to a small, air-filled tennis ball. It is basically a thick-walled, completely hollow particle that can be produced by welding cutting from a tube or a film made of thermoplastic elastomers, similar to a blister film made of polyethylene with separated air chambers and then punching out the hollow particles.
• Multi-layer films or tubes can also be used, which for example have a low-melting layer on the outside and a core with a higher melting point on the inside. Multi-layer films or tubes can be produced using a multi-component extruder directly during extrusion or by subsequent coating using another polymer, a hot melt adhesive or a lower-melting polyurethane.
• Porous molded body
• the invention relates to the use of the hollow particles described above for the production of porous shaped bodies and a process for the production of porous shaped bodies by thermally bonding or gluing these hollow particles.
• the thermal connection can be done by welding with steam or hot air or high-energy waves, in particular microwaves, after prior application of appropriate absorbers, for example polar liquids such as glycerol triacetate.
• the hollow particles have a size comparable to that of commercial particle foams (approx. 2-15 mm in diameter), they can be processed with machines similar to the production of molded parts for particle foams. If the hollow bodies are larger, processing by gluing or foaming is preferred. Manual processing using cold welding is also possible.
• the porous moldings obtainable by this process preferably have a density in the range from 50 to 500 kg / m 3 , particularly preferably in the range from 100 to 300 kg / m 3 .
• Polymeric binders such as melamine-formaldehyde resins, polyurethane resins, polyester resins or epoxy resins are suitable as binders.
• Such resins are for example in Encyclopedia of Polymer Science and Technology (Wiley ) can be found under the following chapters: a) Polyesters, unsaturated: Edition 3, Vol. 11, 2004, pp. 41-64 ; b) Polyurethanes: Edition 3, Vol. 4. 2003, pp. 26-72 and c) Epoxy resins: Edition 3, Vol. 9, 2004, pp. 678-804 . Furthermore, in Ullmann's Encyclopedia of Industrial Chemistry (Wiley) following chapters : a) Polyester resins, unsaturated: Edition 6, Vol. 28, 2003, pp.
• the binders can be used in the form of solutions or dispersions. Preference is given to using binders which are compatible with the hollow particles and have comparable mechanical properties.
• the binder particularly preferably has an elongation at break of at least 50% and a tensile strength of at least 5 MPa.
• the proportion of hollow particles is preferably in the range from 60 to 90% by weight, based on the porous shaped body.
• the porous molded body preferably consists essentially of hollow particles and a matrix of polyurethane, so that a proportion of preferably 10 to 40% by weight of polyurethane adhesive used or polyurethane matrix formed, based on the porous molded body, results.
• porous moldings are produced in which the hollow particles are embedded in a matrix formed from a polyurethane adhesive. It is also possible, by gluing with a foamable polyurethane mixture, to obtain porous molded bodies in which the hollow particles are embedded in a matrix made of a polyurethane foam.
• the matrix made of polyurethane or polyurethane foam is preferably formed from at least one aromatic diisocyanate and at least one polyol.
• the polymer matrix consists of a polyurethane foam
• a 'foam-in-foam' shaped body which consists of a dense bed of hollow particles, the spaces in between being filled with foam.
• the matrix particularly preferably consists of a polyurethane foam if a particularly low thermal conductivity is to be achieved.
• the polyurethane foam matrix is preferably closed-cell, i. they have a closed cell content of at least 90%, preferably at least 95%.
• the porous moldings according to the invention preferably contain, as matrix, foamed or unfoamed polyurethanes, which can be obtained by reacting isocyanates with isocyanate-reactive compounds, optionally in the presence of blowing agents.
• the mixture of the components for producing the polyurethane matrix is also referred to below as a reactive polyurethane mixture. It is preferred to use components which are known to the person skilled in the art for the production of polyurethane elastomers.
• thermoplastic polyurethanes are suitable components for the polyurethane binder.
• Preferred isocyanates for the binder are diphenylmethane diisocyanates (MDI), in particular 4,4'-MDI, 2,4'-MDI, polymeric MDI, TDI, HDI, trimerized HDI, IPDI, H12MDI and mixtures thereof.
• MDI diphenylmethane diisocyanates
• PMDI polymeric MDI
• the polymeric MDI (PMDI) used are in particular those with a viscosity of 10-10,000 mPas, in particular 20-5,000 mPas, measured at 25 ° C. in accordance with DIN53018. Very particularly preferred types have a viscosity between 50 and 1,000 mPas.
• Preferred isocyanate-reactive compounds are 2-3-functional polyols such as polypropylene glycols (Lupranol® 1000, Lupranol® 1100 and Lupranol® 1200) with average molecular weights Mw in the range of 200-5000 g / mol, polytetrahydrofuran, aliphatic polyester polyols with average molecular weights Mw in the range of 500 - 3000, flexible foam polyols or castor oil are used.
• the chain extenders used are preferably butanediol, ethylene glycol, ethylene glycol, triethylene glycol, propylene glycol or dipropylene glycol.
• TMP glycerine or short-chain amines are preferably used as crosslinkers.
• Chain extenders, crosslinking agents or mixtures thereof are expediently used in an amount of 1 to 20% by weight, preferably 2 to 5% by weight, based on the polyol component.
• the polyurethane foam matrix is usually produced in the presence of blowing agents.
• the blowing agent used is preferably water, which reacts with isocyanate groups to split off carbon dioxide.
• Another widely used chemical blowing agent is formic acid, which reacts with isocyanate to release carbon monoxide and carbon dioxide.
• So-called physical blowing agents can also be used in combination with or instead of chemical blowing agents. These are compounds that are inert towards the components used, are mostly liquid at room temperature and evaporate under the conditions of the urethane reaction. The boiling point of these compounds is preferably below 50 ° C.
• the physical blowing agents also include compounds that are gaseous at room temperature and are introduced into or dissolved in the starting components under pressure, for example carbon dioxide, alkanes, in particular low-boiling alkanes and fluoroalkanes, preferably alkanes, in particular low-boiling alkanes and fluoroalkanes.
• the physical blowing agents are mostly selected from the group containing alkanes and / or cycloalkanes with at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals, fluoroalkanes with 1 to 8 carbon atoms, and tetraalkylsilanes with 1 to 3 carbon atoms in the alkyl chain, in particular tetramethylsilane.
• Examples include propane, n-butane, iso- and cyclobutane, n-, iso- and cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl formate, acetone, and fluoroalkanes, which can be broken down in the troposphere and therefore for the ozone layer are harmless, such as trifluoromethane, difluoromethane, 1,1,1, 3,3-pentafluorobutane, 1,1,1, 3,3-pentafluoropropane, 1,1,1, 2,3-pentafluoropropene, 1-chloro 3,3,3-trifluoropropene, 1,1,1,2-tetrafluoroethane, difluoroethane and 1,1,1, 2,3,3,3-heptafluoropropane, and perfluoroalkanes, such as C3F8, C4F10, C5F12, C
• a mixture of physical and chemical blowing agents can be used.
• Mixtures of physical blowing agents and water, in particular of hydrocarbons and water, are particularly preferred.
• hydrocarbons the pentanes, and here in particular the cyclopentane, are particularly preferred.
• the polyisocyanates and the compounds having at least two hydrogen atoms reactive with isocyanate groups are reacted in such amounts that the isocyanate index in the case of the polyurethane foams is in a range between 100 and 220, preferably between 115 and 180 .
• the polyurethane foams can be produced batchwise or continuously with the aid of known mixing devices.
• an index of> 180, preferably 300-400, can also be used.
• the starting components can be mixed with the aid of known mixing devices.
• the polyurethane foams are usually produced by the two-component process.
• the compounds with at least two isocyanate-reactive hydrogen atoms, the blowing agents, the catalysts and the other auxiliaries and / or additives are mixed to form a so-called polyol component and these are mixed with the polyisocyanates or mixtures of the polyisocyanates and optionally blowing agents, also as an isocyanate component referred to, implemented.
• the starting components are usually mixed at a temperature of from 15 to 50.degree. C., preferably from 20 to 30.degree.
• the reaction mixture can be mixed with high or low pressure metering machines.
• the density of the rigid foam matrix obtained here is preferably 30 to 500 kg / m 3 .
• the hollow particles can, for example, be initially charged in such a way that they cannot subsequently be pressed apart or cannot be pressed apart to any significant extent by the foamed or unfoamed polyurethane reactive resin mixture.
• a tightly closable form filled to the brim with a tightly packed bed or a double-belt laminator, in which the height of the bed corresponds to the processing height of the laminator is suitable.
• the foamed or non-foamed polyurethane reactive resin mixture is added in such a way that a weight fraction of 20 wt.%, Preferably 15 wt.
• the hollow particles are stirred with the reactive polyurethane mixture, brought into the appropriate shape and cured.
• the blowing agent-containing polyurethane reactive mixture is poured evenly over the bulk of the hollow particles and allowed to react without the individual hollow particles being able to be pressed apart appreciably by the foaming process.
• Foamable reactive polyurethane mixtures should be characterized by high flowability and a relatively long reaction time so that the cavities between the individual hollow particles can be wetted by the flowable reactive polyurethane mixture and filled during foaming. Sufficiently long reaction times can be set by the type and amount of the catalysts used. In order to achieve a sufficiently high hardening of the reaction mixture even with low amounts of catalyst or completely without catalyst, the mold in which the reaction takes place can be heated to correspondingly high temperatures.
• the foam system used is foamed in an open mold, it should have a thread-pulling time of at least 60 seconds, preferably at least 90 seconds and particularly preferably at least 120 seconds.
• a mixture of amine catalysts customary in polyurethane can be used, for example, in order to achieve comparable reaction times.
• the hollow particles Before bonding, the hollow particles can be coated with various additives, such as e.g. Flame retardants, catalysts.
• additives such as e.g. Flame retardants, catalysts.
• Foams can be produced from the hollow particles used according to the invention, for example by welding them together in a closed mold under the action of heat. To do this, the particles are filled into the mold and, after the mold has been closed, steam or hot air is introduced, which causes the particles to expand somewhat and weld together to form foam, preferably with a density in the range from 30 to 600 g / l.
• the foams can be semi-finished products, for example panels, profiles or webs, or finished molded parts with simple or complex geometry. Accordingly, the term includes TPU foam, foam semi-finished products and foam molded parts.
• the temperature during the welding of the TPU hollow particles is preferably between 100 ° C and 160 ° C.
• the present invention thus also relates to processes for producing foam based on thermoplastic polyurethane, the expanded thermoplastic polyurethane according to the invention being welded to a molded body by means of steam at a temperature between 100 ° C. and 160 ° C.
• the invention also relates to the use of the hollow particles for producing TPU foams, as well as TPU foams, obtainable from the hollow particles.
• the foams according to the invention can be thermoplastically recycled without any problems.
• the hollow particles are extruded using an extruder with a degassing device, with the extrusion optionally being preceded by mechanical comminution. They can then be reprocessed into hollow particles or foams in the manner described above.
• the porous shaped body according to the invention can be laminated on at least one side with at least one cover layer in order to improve the properties of the surface, e.g. B. to increase the robustness, to train it as a vapor barrier or to protect against light contamination.
• the cover layers can also improve the mechanical stability of the porous shaped body. If cover layers are used on both surfaces, these can be the same or different.
• cover layers All materials known to the person skilled in the art are suitable as cover layers. They can be non-porous and thus act as a vapor barrier, e.g. B. plastic films, preferably metallized plastic films that reflect thermal radiation. But it can also be used porous cover layers that allow air to penetrate into the material, such as. B. porous films, papers, fabrics or fleeces.
• the surface of the composite material can also be coated with a material in order to change the feel of the composite material.
• an applied layer can improve the adhesion to other substrates.
• the absorption of moisture can be reduced by applying a suitable layer.
• a suitable layer can also consist of a reactive system such as. B. epoxy resins or polyurethanes, which may be applied by spraying, knife coating, pouring or brushing o. ⁇ can be.
• the cover layers can themselves also consist of several layers.
• the cover layers can be attached with the polyurethane reactive mixture that is used to produce the matrix, but another adhesive can also be used.
• the surface of the composite material can also be closed and solidified by introducing at least one suitable material into a surface layer.
• suitable material are z. B. thermoplastic polymers, such as. B. polyethylene and polypropylene, or resins such as. B. melamine-formaldehyde resins are suitable.
• the hollow particles used according to the invention lead in further processing by means of gluing or welding to porous moldings which, in terms of their mechanical properties, are similar to those of welded foam beads made of thermoplastic elastomers, such as those in WO 2007/082838 are comparable, but are transparent and thick-walled.
• the method according to the invention offers the possibility of achieving thicker cell walls with a low component weight at the same time.
• the porous moldings according to the invention can be used for a wide variety of applications. Due to the elastomeric properties, it is suitable for applications in the sports, shoe and packaging sectors, for example as soles for sports or safety shoes or as packaging for electronic components or devices.
• the porous molded bodies are preferably used as damping elements in shoes, sports equipment, automobiles or machines.
• Table 1 Short name composition E-TPU1 (Infinergy® 32-100 U10) expanded, predominantly closed-cell foam particles based on thermoplastic polyurethane, obtained by foaming granulated, blowing agent-containing TPU1 under pressure and high temperature, bulk density 110 g / l.
• E-TPU2 Infinergy® 32-150 U10) expanded, predominantly closed-cell foam particles based on thermoplastic polyurethane, obtained by foaming granulated, blowing agent-containing TPU1 under pressure and high temperature, bulk density 150 g / l.
• TPU1 Thermoplastic polyether polyurethane with a Shore hardness of 80A based on PTHF1000, 1,4 butanediol, 4,4 'MDI TPU2
• the density of the porous moldings was determined in accordance with DIN EN ISO 1183-1, A.
• the compressive strength of the porous moldings was measured based on DIN EN ISO 3386 at 10%, 25%, 50% and 75% compression.
• the compression set of the porous moldings was measured after conditioning (6h / 50 ° C. / 50%) according to ASTM D395.
• Zone 1 180 ° C
• Zone 2 190 ° C
• Zone 3 200 ° C
• Zone 4 190 ° C
• hose head 190 ° C (TPU1) or 200 ° C (TPU2)
• Transparent tubes with an outside diameter of 5.4 mm and a wall thickness of 1.0 mm, as well as transparent tubes with an outside diameter of 5.0 mm and a wall thickness of 0.2 mm were produced on the laboratory extruder from TPU1 and TPU2.
• the thin-walled tubes obtained were processed into tetrahedra with an edge length of 12 mm using a Qigg brand laboratory welder, and the thick-walled tubes were processed into cylinders with an average length of 15 mm using film welding tongs from Kapp.
• the hollow particles HP1 to HP3 or the comparison products E-TPU1 and E-TPU2 were mixed with an additional 20 and 30 parts by weight of the 2-component PU adhesive K1 and to form cube-shaped, porous moldings with a Edge length of 44 mm processed.
• the hollow particles HP1 to HP3 or the comparative products E-TPU1 and E-TPU 2 were placed in a PE container, the corresponding amounts of components 1 and 2 of adhesive 1 were weighed out, mixed intensively, placed on the hollow particles and mixed intensively with them and put the mixture in a hinged mold with an inner edge length of 44 mm. After the adhesive had cured, the molding was removed from the mold and the density was determined using the method described above. Table 1.
• the moldings of Examples B1 to B3 according to the invention show a significantly higher compressive strength compared to the comparative tests V1 and V2 and a lower resistance to compression made from thermoplastic elastomers and porous moldings

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